Hydrogenation catalyst and preparation method thereof and preparation method of tetrahydrofurfuryl alcohol

Abstract

The invention relates to the field of tetrahydrofurfuryl alcohol production, in particular to a hydrogenation catalyst and its preparation method and a preparation method of tetrahydrofurfuryl alcohol. The hydrogenation catalyst contains a carrier and a ruthenium component loaded on the carrier. The preparation method of the hydrogenation catalyst comprises the following steps: 1) conducting coprecipitation on a mixed aqueous solution containing a titanium oxide precursor, a zinc oxide precursor and a zirconia precursor, and washing and drying the obtained precipitate, and successively molding, drying and roasting carrier powder obtained after drying so as to prepare the carrier; and 2) adding the carrier prepared in the Step 1) into a water solution of a ruthenium precursor, adding alkaline lye, controlling pH value to 6-9, stirring until a black solid is generated, and successively washing, drying and roasting the black solid. The hydrogenation catalyst of the invention has high activity and selectivity, is applicable to continuous preparation of furfuryl alcohol, and is still highly-efficient in reacting under the solvent-free condition. Thereby, separation of a solvent is avoided, production process is simplified, and costs are lowered.

Description

technical field

[0001] The invention relates to the field of furfuryl alcohol production, in particular to a hydrogenation catalyst, a preparation method thereof and a preparation method of tetrahydrofurfuryl alcohol. Background technique

[0002] Tetrahydrofurfuryl alcohol is an important chemical raw material with a wide range of uses, not only as an important organic synthesis intermediate for the synthesis of succinic acid, glutaric acid, tetrahydrofuran, lysine, long-acting vitamins, furan and pyridine , and is an excellent solvent, plasticizer, decolorizer and deodorant.

[0003] At present, tetrahydrofurfuryl alcohol is mainly produced industrially through a two-step process. First, furfural is subjected to selective hydrogenation to obtain furfuryl alcohol, and then further selective hydrogenation of furfuryl alcohol is used to prepare tetrahydrofurfuryl alcohol. But because of higher unit consumption (industrial production 1 ton of tetrahydrofurfuryl alcohol consum...

Examples

preparation example Construction

[0020] In a second aspect, the present invention provides a method for preparing the above hydrogenation catalyst, characterized in that the method comprises:

[0021] 1) Co-precipitate the mixed solution of titanium oxide precursor, zinc oxide precursor and zirconium oxide precursor, wash and dry the obtained precipitate, and shape, dry and roast the carrier powder obtained after drying to prepare carrier;

[0022] 2) Add the carrier prepared in step 1) to the aqueous solution of the ruthenium precursor, then add the alkali solution, control the pH value to 6-9, stir until a black solid is formed, and wash and dry the obtained black solid in sequence and roasting.

[0023] In the present invention, the mixed solution can be prepared by conventional preparation methods in the art. Preferably, the aqueous solution containing the precursor of titanium oxide, the aqueous solution containing the precursor of zinc oxide and the aqueous solution containing the precursor of zirconiu...

Embodiment 1-7

[0048] Prepare 1M TiCl with a pH value of 0.5 4 solution (adjust the pH value with hydrochloric acid), 1.5M Zn(NO 3 ) 2 ·6H 2 O solution and 1.5M ZrOCl 2 ·8H 2 O solution, and then accurately measure the above four solutions according to the component content of the catalyst to form a titanium-zinc-zirconium mixed liquid. The amounts of the various solutions are such that the content of each component in the final prepared catalyst satisfies the values ​​shown in Table 1. Add an appropriate amount of deionized water into the reaction kettle, and under constant stirring, add the silicon-nickel-calcium-zirconium mixed solution and 1M sodium carbonate solution into the reactor in parallel to control the reaction pH value to 8.0. The temperature was raised to 60°C. After the feeding was completed, the heat preservation and stirring was continued for 1 hour until the precipitate was formed. The precipitate was filtered and washed five times, and dried at 110°C for 12 hours to ...

Embodiment 8-14

[0059] The reaction is carried out in a stainless steel reactor to prepare tetrahydrofurfuryl alcohol. Specifically, the hydrogenation catalyst and furfural prepared in the above examples 1-7 are respectively selected for reaction, the reaction temperature is 105 ° C, the hydrogen pressure is 2 MPa, and the furfural liquid space Speed ​​0.2hr -1 , the hydroaldehyde molar ratio is 15. After the reaction was stable, the reaction result was analyzed by gas chromatography, and the conversion rate of furfural and the selectivity of tetrahydrofurfuryl alcohol were shown in Table 2 below.

technical field

[0001] The invention relates to the field of furfuryl alcohol production, in particular to a hydrogenation catalyst, a preparation method thereof and a preparation method of tetrahydrofurfuryl alcohol. Background technique

[0002] Tetrahydrofurfuryl alcohol is an important chemical raw material with a wide range of uses, not only as an important organic synthesis intermediate for the synthesis of succinic acid, glutaric acid, tetrahydrofuran, lysine, long-acting vitamins, furan and pyridine , and is an excellent solvent, plasticizer, decolorizer and deodorant.

[0003] At present, tetrahydrofurfuryl alcohol is mainly produced industrially through a two-step process. First, furfural is subjected to selective hydrogenation to obtain furfuryl alcohol, and then further selective hydrogenation of furfuryl alcohol is used to prepare tetrahydrofurfuryl alcohol. But because of higher unit consumption (industrial production 1 ton of tetrahydrofurfuryl alcohol consum...

Examples

preparation example Construction

[0020] In a second aspect, the present invention provides a method for preparing the above hydrogenation catalyst, characterized in that the method comprises:

[0021] 1) Co-precipitate the mixed solution of titanium oxide precursor, zinc oxide precursor and zirconium oxide precursor, wash and dry the obtained precipitate, and shape, dry and roast the carrier powder obtained after drying to prepare carrier;

[0022] 2) Add the carrier prepared in step 1) to the aqueous solution of the ruthenium precursor, then add the alkali solution, control the pH value to 6-9, stir until a black solid is formed, and wash and dry the obtained black solid in sequence and roasting.

[0023] In the present invention, the mixed solution can be prepared by conventional preparation methods in the art. Preferably, the aqueous solution containing the precursor of titanium oxide, the aqueous solution containing the precursor of zinc oxide and the aqueous solution containing the precursor of zirconiu...

Embodiment 1-7

[0048] Prepare 1M TiCl with a pH value of 0.5 4 solution (adjust the pH value with hydrochloric acid), 1.5M Zn(NO 3 ) 2 ·6H 2 O solution and 1.5M ZrOCl 2 ·8H 2 O solution, and then accurately measure the above four solutions according to the component content of the catalyst to form a titanium-zinc-zirconium mixed liquid. The amounts of the various solutions are such that the content of each component in the final prepared catalyst satisfies the values ​​shown in Table 1. Add an appropriate amount of deionized water into the reaction kettle, and under constant stirring, add the silicon-nickel-calcium-zirconium mixed solution and 1M sodium carbonate solution into the reactor in parallel to control the reaction pH value to 8.0. The temperature was raised to 60°C. After the feeding was completed, the heat preservation and stirring was continued for 1 hour until the precipitate was formed. The precipitate was filtered and washed five times, and dried at 110°C for 12 hours to ...

Embodiment 8-14

[0059] The reaction is carried out in a stainless steel reactor to prepare tetrahydrofurfuryl alcohol. Specifically, the hydrogenation catalyst and furfural prepared in the above examples 1-7 are respectively selected for reaction, the reaction temperature is 105 ° C, the hydrogen pressure is 2 MPa, and the furfural liquid space Speed ​​0.2hr -1 , the hydroaldehyde molar ratio is 15. After the reaction was stable, the reaction result was analyzed by gas chromatography, and the conversion rate of furfural and the selectivity of tetrahydrofurfuryl alcohol were shown in Table 2 below.